Study of Prussian Blue (PB) films by ac-electrogravimetry: influence of PB morphology on ions movement

The electrochemical response of Prussian Blue films in NaCl solutions was studied. It was proved that the stability with cycling of PB films increased when these films are covered with a Nafion® membrane. This fact allows PB films to be studied in NaCl solutions under steady state conditions by impedance spectroscopy and ac-electrogravimetry. A model, which can explain the differences between the electrochemical behaviour of amorphous PB films and crystalline PB films in NaCl solutions, is proposed. This model is based on the hypothesis of a partial dehydration of the sodium ions before the electrochemical reactions take place, allowing the transport of sodium ions through the zeolitic chan…

Surface structure determination by SEM image processing and electrochemical impedance of graphite+polyethylene composite electrodes

Abstract The electrochemical impedance behaviour of heterogeneous or/and rough electrodes has usually been associated with some geometrical parameters of the surface structure or to a statistical description of the surface properties. An experimental method for sample preparation of graphite + polyethylene composite electrodes based on plasma etching is proposed. After plasma etching, the statistical properties of the electrode, such as the graphite particle size distribution and fractional coverage are measured from scanning electron microscopy pictures using image processing software. The statistical information obtained for the surface is combined with impedance equations of independent …

Comments on the paper entitled ‘The formulation and modelling of the anodic dissolution of zinc through adsorbed intermediates’by G.G. Láng, and G. Horányi [J. Electroanal. Chem. 583 (2005) 148–154]

The points raised in the paper entitled "Comments on the paper entitled 'The formulation and modelling of the anodic dissolution of zinc through adsorbed intermediates"' have been discussed. It has been shown that, in contrast to the statements in the "Comments", most of the papers concerning the reaction schemes suggested for the interpretation of the dissolution or deposition of metals, which were considered as a support for the opinion of the Authors of the "Comments", support the views expressed in our original paper [J. Electroanal. Chem. 583 (2005) 148]. On the other hand, it has been stressed again that the criticism expressed in the original paper refers to dubious conclusions drawn…

A kinetic interpretation of a negative time constant in impedance equivalent circuits for the dissolution/passive transition

Abstract A theoretical impedance function is proposed for the active/passive transition of nickel in an acid sulphate medium. It is considered that passivating species progressively covers the electrode surface. This approximated model predicts the appearance of negative time constants in the impedance spectra when coverage coefficient θ values for passive species are greater than 0.5.

Study by EQCM on the voltammetric electrogeneration of poly(neutral red). The effect of the pH and the nature of cations and anions on the electrochemistry of the films

Generation of poly(neutral red) films has been studied by means of the simultaneous measurements of current–potential and mass–potential curves during cyclic voltammetry (CV) experiments. It has been proved that the presence of molecular oxygen in the solution increases the amount of polymer deposited on the electrode. Otherwise, using the mass/charge ratio it is possible to obtain quantitative information about the electrodeposition by different procedures. It is observed that this ratio decreases when the amount of polymer electrogenerated increases, except when the polymer is not reduced and oxidised after its electrogeneration. The study of poly(neutral red) by CV and quartz crystal mic…

An electrochemical quartz crystal microbalance study of lithium insertion into thin films of tungsten trioxide I. Modeling of the ionic insertion mechanism

A theoretical description of the mechanism of lithium insertion into amorphous thin films of tungsten trioxide (a-WO3) prepared by thermal vacuum evaporation of WO3 powder is presented. The model developed is based on the experimental results obtained by chronoamperometry and ac impedance spectroscopy associated with electrochemical quartz crystal microbalance (EQCM). The electrode mass change and the current flowing through the electrochemical cell during cathodic polarization are simulta neously recorded. As expected, it can be observed that the insertion process is associated with a gain of mass of the inserted electrode at long times (t > 1 s). On the other hand at short times (t < 1 s)…

A New Insight in the Electrochemical Response of a Depassivated Surface

An electrochemical quartz crystal microbalance study of lithium insertion into thin films of tungsten trioxide II. Experimental results and comparison with model calculations

Abstract Lithium insertion into amorphous thin films of tungsten trioxide (a-WO 3 ) prepared by thermal vacuum evaporation of WO 3 powder has been studied experimentally by chronoamperometry, cyclic voltammetry and ac impedance spectroscopy associated with electrochemical quartz crystal microbalance (EQCM). During cathodic polarization of the electrode and at short times two antagonistic processes occur. One is a non faradaic process and is associated with the expulsion of anions from the electrode surface under the effect of the electric field built in the electrolyte when a potential difference is imposed between the electrodes. The other one is the faradaic insertion of non-solvated lith…

An electrochemical impedance and ac-electrogravimetry study of PNR films in aqueous salt media

Electrochemical impedance spectra and ac-eletrogravimetry of poly(neutral red) films are studied in different aqueous media. The dependence of these experimental data on the nature of alkaline cation and monovalent anion present in the solution and on the pH is analysed. During the electrochemical processes, it is observed that all three species—the salt cation, the salt anion and the hydronium ion—participate to balance the electrical charge within the film. It is also possible to conclude that the participation of anions takes place faster than hydronium ions participation. Besides, the relative participation of these species is related to the pH of the solution. Keywords: Poly (neutral r…

Laser depassivation of a channel flow double-electrode: A new technique in repassivation studies

Abstract A powerful tool for distinguishing between the different electrochemical steps involved during a depassivation-repassivation sequence was developed by combining the pulsed laser depassivation technique with an hydrodynamic electrochemical method: the channel flow double-electrode (CFDE). This experiment consisted of transporting the chemical species (Fe 2+ ) released by a depassivated iron electrode to a collecting electrode where these species were oxidized. A qualitative idea of the relative contribution of the anodic dissolution to the repassivation behavior was obtained. For a passive iron in acidic solution it was found that about 15% of the total charge is related to anodic d…